KR101105075B1 - Solder pastes comprising nonresinous fluxes - Google Patents

Solder pastes comprising nonresinous fluxes Download PDF

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KR101105075B1
KR101105075B1 KR1020087011010A KR20087011010A KR101105075B1 KR 101105075 B1 KR101105075 B1 KR 101105075B1 KR 1020087011010 A KR1020087011010 A KR 1020087011010A KR 20087011010 A KR20087011010 A KR 20087011010A KR 101105075 B1 KR101105075 B1 KR 101105075B1
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South Korea
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gel
paste
solder
method
soldering
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KR1020087011010A
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Korean (ko)
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KR20080071984A (en
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크리스티안 로스츠
프랑크 브레르
볼프강 슈미트
토마스 크레브스
외르크 트로들러
위르겐 호르눙
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헤레우스 머티어리얼즈 테크놀로지 게엠베하 운트 코 카게
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Priority to DE102005053553A priority Critical patent/DE102005053553A1/en
Priority to DE102005053553.4 priority
Application filed by 헤레우스 머티어리얼즈 테크놀로지 게엠베하 운트 코 카게 filed Critical 헤레우스 머티어리얼즈 테크놀로지 게엠베하 운트 코 카게
Priority to PCT/EP2006/010139 priority patent/WO2007054198A2/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3612Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
    • B23K35/3618Carboxylic acids or salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3612Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/362Selection of compositions of fluxes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805Shape
    • H01L2224/4809Loop shape
    • H01L2224/48091Arched
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481Disposition
    • H01L2224/48151Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item

Abstract

The present invention relates to a resin-free solder paste comprising metal powders, in particular solder and gels, wherein the gels according to the invention do not leave residues on the metal surface upon melting of the metal powders. The gel according to the invention consists of a mixture capable of stable storage comprising carboxylic acids, amines and solvents. Key applications include power modules, die attach, chip-on-board, system-in-package (SiP), wafer bumping, especially under bump metallization ( Application of solder paste to UBM, Under-Bump-Metallization and Surface-Mounted Technology (SMT) and especially lacquered circuits. With the resin-free solder paste according to the invention, no cleaning is required after the protective lacquer coating after the soldering of the electrical connections and the pore formation in the solder bumps applied to the UBM is reduced to less than 20 Vol.%.

Description

Soldering paste with resin-free solvent {SOLDER PASTES COMPRISING NONRESINOUS FLUXES}

The present invention relates to the application of a new gel consisting of a mixture of carboxylic acids, amines and solvents, pastes, in particular a metal component as powder, including a solder paste in which the gel is dispersed, and the application of solder paste to Under-Bump-Metallization (UBM). And power modules, die attach, Chip-on-Board, System-in-Package (SiP), Wafer Bumping, or Surface Mounted Technology (SMT), especially lacquered circuits To the use of such a solder paste.

German patent DE 841 097 discloses a braze in which amines are enriched in ureide with carboxylic acids. According to the German patent DE 841 097 carboxylic acids and amines are present in the mixture. However, these materials chemically bond with each other and form, for example, ureides.

German patent DE 41 19 012 discloses a solder paste which is washable with water, which consists of an adhesive-flux mixture comprising a water-soluble salt of a fatty-amine comprising lead powder, carboxylic acid and a solvent. .

It is an object of the present invention to minimize residue formation in soldered parts.

Also, Wafer Bumping: Is the Industry Ready? The pores according to (Greg Reed, Reed Media Services, Gurnee, III.-10/1/2004-Semiconductor International) are generally not desirable, and there is a need to maximize pore formation in all soldered portions. In this regard it is an object of the present invention to reduce pore formation below a maximum of 20% by volume, in particular below 15% by volume. It is also desirable to ensure coplanar bumps as much as possible, so the object of the present invention is to ensure this.

In the present invention, the carboxylic acid and the amine gel together with the polar solvent, and salt formation or chemical reaction of the amine with the carboxylic acid is suppressed.

The solution according to the invention is described in the independent claims. The dependent claims describe preferred embodiments.

In the present invention there is provided a resin-free soldering paste comprising metal powder, in particular solder and gel, wherein the gel according to the invention does not leave residue on the metal surface upon melting of the metal powder. The gel according to the invention consists of a mixture capable of stable storage comprising carboxylic acids, amines and solvents. Key applications include power modules, die attach, chip-on-board, system-in-package (SiP), wafer bumping, especially under bump metallization ( UBM) and surface mounted technology (SMT) and in particular the application of solder paste to lacquered circuits. With the resin-free solder paste according to the present invention, no cleaning is required after the protective lacquer coating after soldering the electrical connections and the pore formation in the solder bumps applied to the UBM is reduced to less than 20% by volume.

Gels according to the invention are dissolved in carboxylic acids and amines. The main component is therefore a gelled solution comprising amines, carboxylic acids and solvents. The carboxylic acid component consists of at least one carboxylic acid and is especially a mixture of various carboxylic acids. The amine component consists of at least one amine and is in particular a mixture of various amines. The solvent component consists of at least one solvent and in particular an organic solvent.

In order to inhibit the reaction of the amine with the carboxylic acid, a low temperature such as, for example, room temperature is preferred, and the components are mixed with each other as quickly as possible. Thus gelation consists of an auxiliary valence family, in particular hydrogen bonds. The solution or gel may contain other substances, such as thickeners, for example.

Thus, in the present invention, it is possible to suppress the flux residue after the soldering of the solder paste. Significant process improvements are achieved, especially when using solder pastes that require cleaning of residues in the solder. To date, cleaning costs can exceed paste costs. In particular, a simplification is made on how other processes follow the soldering process. Additional electrical inspection, for example by means of additional bonding or needle testers, is simplistically simplified. Lacquered circuits do not require lacquer resistance to flux residues so far required.

In the present invention, processes in power modules, die attach, wafer bumping, system-in-package, dynamic random access memory (DRAM), automotive applications are simplified and further improved in quality. This provides a significant environmental benefit as well, as waste is reduced or significant cleaning costs and thus the use of cleaning agents are reduced.

Within the scope of the present invention it has been found that the composition of the resin or rosin-based paste changes in relation to the metal content of the flux, especially when applied to the UBM with a doctor blade, which the inventors have found to be subject to high standard deviations related to pore formation. Report at least one cause for predicting the relationship between the maximum porosity of 30% by volume and greater volume% and heterogeneous composition. In addition, the solid content of the lead-free solder paste is limited to 90% by weight.

The solution in the manufacture of wafer bumps is to disperse the solder powder in the gel. Pastes comprising lead powder dispersed in a gel comprise levels of lead powder in excess of 90% by weight, in particular 91% by weight. The volume ratio of the lead powder and paste is at least 55% by volume, in particular at least 60% by volume.

The use of the flux according to the invention is not limited to lead payment. Gels that can be quickly processed into pastes are also suitable for the production of other pastes. The flux according to the invention can be used not only as a gel but also as a lubricant.

In the present invention, it is possible to prepare a gel that can be stably stored. Such a gel can be removed at a temperature between 150 ° C and 250 ° C. Due to their storage stability, gels or pastes made from gels are easy to handle during the period between gel preparation and its use. What is important in this regard is that the gel lasts for several months. Preferably the consistency of the gel hardly changes under normal storage conditions.

The main components of the gel are carboxylic acids, amines and solvents which can be easily removed via heat. This component is volatilized or decomposed essentially between 150 ° C and 250 ° C, leaving no residue. Adjuvants may be added. The use of additives to control fluidity has proven to be somewhat effective. The dye is preferably added in the ppm range. Certified additives also include, for example, decomposition promoters such as peroxides or active agents such as halogen activators, in particular ammonium chloride.

In a preferred embodiment

The gel is degradable by heat or almost no residue,

The gel is similar to, for example, rosin or resin in terms of viscosity and adhesion,

The solvent stabilizes the gel state,

The solvent inhibits the chemical reaction between the carboxylic acid and the amine,

Polar solvents form hydrogen bonds,

The polar solvent comprises, for example, a polyol such as glycol or glycerin,

Carboxylic acids are used for the separation or removal of metal oxides, in particular tin oxides, in lead powders,

Activators are used for the separation or removal of metal oxides, in particular tin oxides, from lead powders,

-Carboxylic acid is easily decomposable,

Carboxylic acids are for example multifunctional such as citric acid, adipic acid, cinnamic acid and benzyl acid,

The carboxylic acid comprises from 2 to 50 C atoms and up to 2 aromatic rings,

The amine is a tertiary amine,

The amine comprises 6 to 100 C atoms,

The mass ratio of carboxylic acids is higher than the mass ratio of amines.

According to the present invention, a solder-free solder paste can be prepared. Therefore, in the present invention, it is possible to remove the resin residue. The matrix material according to the invention for solder powder is almost degradable through heat.

The gel can be adjusted with 1 to 5% by weight of thickener in relation to its dominance. Likewise preferred thickeners are degradable via heat. Even when a wax that cannot be completely decomposed is used as a thickening agent, a solderless paste with little residue is produced, and this residue can be adjusted to less than 1% by weight. Also suitable as thickeners are polyamides or amorphous silicic acids. Amorphous silicic acid is loosely deposited on the surface of the solder during the soldering process. At this time, traces of contaminants remain attached to the silicic acid, which can be easily removed without using a solvent.

Almost equal volume of gel and metal powder are mixed to continue processing the gel into a solder paste. Very fine metal powders and bimodal or multimodal metal powders in this regard have proven to be suitable especially when no further thickening agent is used. In the present invention, it is possible to disperse the metal powder in the gel immediately after preparing the gel. The conventional waiting time is not necessary before injecting the metal powder into the flux.

Soldering pastes consisting of 40 to 60 volume% flux and 40 to 60 volume% lead powder have proven to be suitable.

In an improved form according to the invention dye is added to the gel. Pastes with 10-200 ppm phthalocyanine have proven to be suitable. This corresponds to 0.1 to 2 ‰ of phthalocyanine in the flux or gel. Preferably the dye is not soluble in the metal and decomposes in the presence of an organic substrate. Phthalocyanines fully meet this need. Fluorescent dyes are also very suitable. For example, the paste residue remaining in the paste with 1 ppm of fluorescent dye can visualize the fluorescent dye. Particularly suitable are fluorescent dyes which are stabilized by a gel substrate and which are thermally decomposed without stabilization. In this way minimal residues are seen. This not only allows quality checks but also removes the smallest residues that still exist. Fluorescent pigments or dyes with decomposition temperatures between 150 and 250 ° C. have proven to be preferred.

In particular, the present invention has an important meaning in all fields of use where cleaning has been necessary after the soldering process. The use of solder paste is particularly important in the field of power modules, die attach or chip on board. In this field of application a bonding process for electrical contact is carried out after the parts are soldered for mechanical fixation. Residues deposited in the melting process of the soldering paste on the bonding side make bonding impossible or at least make this process very difficult. Therefore, the absence of flux residues on the bonding side is important for the bonding process. In the present invention a bonding process is now possible without the preceding cleaning process.

Another important field of use of the gels and corresponding solder pastes according to the invention is lacquer coating of circuits. Protective lacquers have electrical insulation in addition to their protection against environmental impacts. The durability required so far for lacquers and residues is not required for solder pastes according to the invention that are free of residues or have little residue formation.

The gel comprising the solder paste for application of the solder paste to UBM (under bump metallization) preferably comprises a polar solvent component, in particular a water soluble solvent and a thickening agent based on the aluminum or carboxylic acid component.

Preferably the content of the solder paste in the adjuvant (gelled solvent) is 5-40% by volume. For this purpose polar solvents such as glycerin, glycol, tridecanol, terpineol have proven to be suitable. A plurality of polyols are suitable for use as solvents according to the invention for the purpose as solvents due to their good transport properties and high viscosity. Polar solvents, well known in the preparation of greases, with high viscosity and good transport properties, can also be used as solvents for the purposes according to the invention. In this regard, the fluidity characteristics of the solvent can be adjusted by mixing a plurality of solvents. However, since the viscosity of the solvent is significantly lower compared to the viscosity of a resin such as rosin, for example, the viscosity is lowered compared to a paste containing a resinous flux based on a paste containing a similar metal powder. At the same viscosity, the lead powder content is increased compared to the paste containing the resinous flux. While the content of the solder powder in the paste with the resinous flux is between 87 and 88.5% by weight and the high viscosity of the paste makes it impossible to apply 90% by weight on the wafer with the photoresist, whereas the flux is Due to the paste being a polar solvent, a lead powder content of more than 90% by weight, in particular of more than 91% by weight, is achieved in particular due to gelation through the polar solvent.

The carboxylic acid component functions to separate the oxide film from the brazed metal surface. Therefore, it should be noted that the metal oxide separation function of the carboxylic acid component is hardly degraded due to the presence of other paste components. In particular, the reaction of the salt or carboxylic acid amide with the amine component should be inhibited. It should be noted that the amine component has an activation function, which is not lost due to reaction with other components of the solder paste, in particular its carboxylic acid component.

In particular all known lead powders, for example tin, lead, bismuth, indium, gold or silver series, can be used in the present invention.

Preferably the lead powder comprises in particular 50% by weight and in some cases greater than 90% by weight tin. Silver and copper are suitable alloying components. Typical tin-lead solders and solders containing high amounts of lead may also be used in the present invention.

Preferably powder types below 38 μm, in particular below 25 μm, correspond to grades 4, 5, 6 and below according to ANSI / J-STD-005 or DIN / EN 61190.

Therefore, it can be used for a plurality of UBMs coated with lead pastes, which lead to 60-90 volume% lead powder, 10-40 volume% polar solvent, 0-20 volume% tertiary amine and 0-20 volume per UBM. % Carboxylic acid. In a preferred embodiment

More than 70% by volume of lead powder,

The sum of the volumes of the amine component and the carboxylic acid component is 10-20% by volume,

The polar solvent is 20-30% by volume.

In particular, the polar solvent is the main component of the flux, ie the main component of the gel present in the paste. In the present invention, due to the high volume fraction of the solder powder in the paste, pore formation is ensured during application and the paste composition, which remains almost constant during application, is achieved through a plurality of solder deposits, especially in UBM. Since the uniformity of the composition remains almost constant under normal processing conditions, the porosity generated is limited to up to 20% by volume, preferably up to 15% by volume, in the confidence interval of 3 sigma, especially 4 sigma, after melting of the solder paste.

It is assumed that the good transport properties of the solvent and the high viscosity have a positive effect on the stability of the paste with high lead powder content. Surprisingly, the reaction between the amine component and the carboxylic acid component through the polar solvent is suppressed, so that the solder paste usable in the present invention has storage stability. Preferably the braze paste contains only a little or preferably no reaction product of the carboxylic acid with the amine.

More preferably, the paste comprises a gel in which the lead powder is dispersed, in particular a gel which is free of resin or resin. When distributing a paste containing gel as a flux to a doctor blade, the paste composition is kept constant, unlike a paste containing a resinous flux, and a uniform solder distribution is applied to a plurality of UBMs when the paste is uniformly applied. . This enables the production of hibernating bumps and reduces the formation of large pores.

The UBM is metallic and, in some cases, an independent connection surface on the wafer surface where no coding through the solder occurs. A plurality of UBMs are placed on the wafer plate, and after the wafer plate is separated into chips, solder placed on the UBM is provided for chip connection according to the regulations. In a preferred method for applying the solder paste to the UBM, the soldering paste is applied to the photoresist or through a scriber, in particular via a printing technique via a doctor blade. In another method, the solder paste is applied to the UBM via a suitable dispenser, for example in jet technology.

The present invention is explained in detail through the following experimental example based on the drawings.

1 shows a solder where traces of residue are visualized through the dye.

Figure 1a is a state does not contain a dye,

Figure 1b is a state containing the dye,

Figure 1c is a state that does not contain a fluorescent dye,

1D shows a state in which a fluorescent dye is included.

2 to 2a shows a power module,

2B and 2C are enlarged partial views of the bonding surface, and in the comparative example of FIG. 2C, the bonding surface is contaminated.

3 shows a lacquered circuit.

4 shows a sketch of a chip die attach with an enlarged carrier on which a chip is fixed.

5 shows a memory card in which a portion of the contact strip is enlarged.

6 shows a histogram of the wafer after melting of the solder paste applied between the photoresists of the UBM according to Table 1. FIG.

7 is an alternative illustration of the results of Table 1, shown as Scatterplot.

FIG. 8 is another alternative plot of the results in Table 1, shown as a box and whisker plot.

9, 10, 11, and 12 show comparative examples of FIGS. 6 and 8 according to Tables 2 and 3.

Experimental Example  One

67% by weight of tridecanol, 20% by weight of cinnamic acid, 10% by weight of tertiary C16 amine fraction and 3% of wax were mixed in a container at room temperature until the gel form was reached. . The gel was then treated with solder paste with solder powder in the usual way. The gel does not require any other waiting time before processing with solder powder.

Experimental Example  2

67% by weight tridecanol, 20% by weight cinnamic acid, 10% by weight tertiary C16 alkylamine fraction, 3% castor oil ester and 0.01% by weight phthalocyanine until the gel form is reached (phthalocyanine) (Hostatint Gruen GG 30) was mixed in a vessel at room temperature. The gel was then treated with solder paste with solder powder in the usual way. The gel does not require any other waiting time before processing with solder powder.

Experimental Example  3

53 wt% tridecanol, 14 wt% terpineol, 10 wt% tertiary C12 alkylamine fraction, 20 wt% sebacic acid and 3 until reaching the gel form state % Castor oil esters were mixed in a vessel at room temperature conditions. The gel was then treated with solder paste with solder powder in the usual way. The gel does not require any other waiting time before processing with solder powder.

Experimental Example  4

67% by weight glycerin, 7% by weight cinnamic acid, 18% by weight tertiary C18 alkylamine fraction, 5% by weight adipic acid, 3% castor oil ester until reaching the gel form And 10 ppm by weight of a fluorescent dye (fluorescent pigment Z-17-N from Dayglo) were mixed in a container at room temperature conditions. The gel was then treated with solder paste with solder powder in the usual way. The gel does not require any other waiting time before processing with solder powder.

Experimental Example  5

25.5 wt% tridecanol, 25 wt% terpineol, 10 wt% tertiary alkylamine (C18 fraction), 30 wt% sebacic acid and 8 wt% benzyl acid until the gel form is reached And 1.5% by weight of adipic acid were mixed in a vessel under room temperature conditions. The gel was then treated with solder paste with 90.5% by weight of solder powder Sn63Pb37 having a particle size range of 5 to 15 μm, according to the general method. The total production time of the paste was within 20 minutes. In this way it was possible to produce very good pastes without other thickeners. The residue could not be identified and was present at least less than 0.1% by weight.

Experimental Example  6

37.5 wt% tridecanol, 28 wt% terpineol, 10 wt% 2-ethyl-4-mentylimidazole, 15 wt% sebacic acid, 8 wt% until reaching a gel form state Benzylic acid and 1.5% by weight of adipic acid were mixed in a vessel at room temperature conditions. In this way very good gel formation could be achieved without other thickening agents. The gel was then treated with solder paste with solder powder in the usual way. The gel did not require any other waiting time before being treated with solder powder and was prepared in a usable form within 20 minutes. After the melting process, no residue could be identified and present at least less than 0.1% by weight.

1a and 1c show the residue 1 in the solder 3 on the substrate 2. 1b and 1d show solder portions of colored fluxes. In this flux the dye 18 is stable only in the residue. Gels prepared according to Experimental Examples 1 to 6 were each mixed with solder paste with the same volume of solder powder. After using the solder paste according to the regulations, the residues 1 were less than 1% by weight, respectively. Residue 1 of the paste according to Experimental Example 2 can be seen in Figure 1b. Residue 1 of the paste according to Experimental Example 4 can be seen in Figure 1d. 1D shows a soldered portion. Fluorescent radiation 5 occurs through UV irradiation 4, which is more clearly shown in FIG. 1C than in FIG. 1C. This allows for automatic detection of very small amounts of residue 1. The adhesive can be adjusted so that the bonding wire is attached and adhered only to the clean side.

2a shows a power module in which a plurality of dies 6 are bonded to the bonding surface 9 via bonding wires 8 in the ceramic plate 7. 2B shows an enlarged bonding surface of the power module. Unlike in the conventional soldering paste of FIG. 2C, this power module is not contaminated due to the residue 1 of the soldering paste upon fixing the part in the particular use of the paste prepared according to one of Examples 1-5. (FIG. 2C). Therefore, the parts can be bonded without cleaning the bonding surface after fixing, because the solder paste residue can be prevented in the present invention and therefore the bonding surface is not contaminated in the present invention.

3 shows a lacquered circuit.

3a shows a circuit according to the invention in which the soldered part is enlarged and no residue is seen in the region of the soldered part.

3B shows a lacquered circuit in which the SMD component 10 is enlarged, with the lacquer 12 present between the components 10 including cracks 14 caused by solder residue in the prior art.

4 shows the solder 3 under the die (active electrical component without housing) 6. The location of the die is indicated by an arrow. The solder 3 is contaminated with flux residue 1 and must first be cleaned for bonding. By using the paste according to the invention, contamination can be significantly reduced, so no cleaning procedure is necessary. This allows for a significant simplification of the process. To date, the costs incurred for cleaning are significantly greater than those incurred in the use of solder pastes.

5 shows an enlarged view of a contact surface 17 consisting of a contact strip 15 of a memory module 16. When soldering components to the substrate, flux is sprayed onto the strip 15 and contaminates the contact surface 17. This causes insufficient contact when inserting the module into the main board. In the present invention, no residue is formed at the contact even when the flux is injected incorrectly, because the flux according to the present invention decomposes almost without residue. This significantly improves the efficiency in the manufacture of memory modules.

Gels are prepared as fluxes in the production of resin and lead-free lead pastes. 53% by weight of tridecanol, 14% by weight terpineol, 10% by weight tertiary C12 alkylamine fraction, 20% by weight sebacic acid and 3% by weight until the gel form is reached in the preparation of the gel The free ester is mixed at room temperature conditions in a vessel. The gel is a 5 such as class (15-25 ㎛) (SA C 4 0 .5), tin-silver-8.5 of the solder paste (95.5% by weight of tin, and 4 wt%, 0.5 wt% of copper) of copper Mixed at a mass ratio of 91.5.

The paste of this composition is applied to the UBM of the wafer through a doctor blade made of hard rubber material in the wafer containing the photoresist. As an alternative it is also possible to apply to the UBM of the wafer via a scriber or screen. After melting of the solder paste applied to the UBM, analysis of the wafer is made regarding the flatness of the bumps and the pore formation of the bumps. The results of the void analysis are summarized in Table 1. The wafer is divided and evaluated into 380 bumps in nine areas each. Maximum porosity is significantly lower than 13.6% by volume, ie 15% by volume. The maximum standard deviation is 2.54 and the mean value of the uniformly formed pores is significantly lower than 5% by volume. A narrow distribution means that there are almost no pores greater than 20% by volume statistically, and that the presence of pores greater than 30% by volume is rare. For comparison a wafer of conventional type, ie a rosin-based flux and 89 wt% solder paste, was prepared. The results achieved with this wafer are summarized in Table 2. 9 and 10 show these results in graphical form. In the case of a paste having a soldering ratio of 90% by weight, it could no longer be applied to the photoresist using a doctor blade because the viscosity of the paste was too high. In another comparative example, the soldering rate of the paste containing the rosin-based flux was 88% by weight. Corresponding results are summarized in Table 3. 11 and 12 show these results in graphical form.

6, 9 and 11 show the frequency of pore grades having a volume of 1% by volume. In the application according to the invention according to FIGS. 1 and 6, a dense maximum is seen in grades 2 to 3 and 3 to 4 volume%, whereas a strong drop in grades 5 to 6 or 6 to 7 and 7 to 8 volume% appear. The proportion exceeding 10% by volume is very small and limited to less than 15% by volume. On the contrary, in the comparative experimental example according to FIG. 9, the maximum value of pores appears in grades 0 to 1 and 1 to 2% by volume, and decreases to a small value in pore grades 3 to 4% by volume but slightly decreases to grades 28 to 29% by volume. . Residual pores of grades above 30% by volume are a significant problem. The second comparative experimental example shown in FIG. 11 shows a form similar to the first comparative experimental example according to FIG. 9.

The scatterplot of FIG. 7 shows the results according to the invention of Table 1, in which the frequency of 380 measurement points each included in measurement groups 1 to 9 of the wafer is specified. It can be seen here that the pore formation between 6 and 10% by volume is very weak and only between 10 and 15% by volume appears individually. This graph shows that in the present invention, pores exceeding 15% by volume are virtually absent, pores exceeding 20% by volume are not expected to appear, and pores exceeding 25% by volume are almost impossible.

In the box and whisker plot according to FIGS. 8, 10 and 12, the range of pores is indicated by lines for each measurement group. Cross represents an average value (average). The depression represents the median, ie the median of the measured values. Bars represent standard deviation (sigma) of the median in both measured value directions.

The present invention can be used for solder paste.

Claims (10)

  1. One or more carboxylic acids that volatilize or decompose without leaving residues between 150 ° C. and 250 ° C., one or more tertiary amines that volatize or decompose without leaving residues between 150 ° C. and 250 ° C., and one or more polar solvents And a reaction product of the carboxylic acid component and the amine component.
  2. The method of claim 1,
    At least one polar solvent is capable of forming hydrogen bonds.
  3. In the gel production method,
    One or more carboxylic acids that volatilize or decompose without leaving residues between 150 ° C. and 250 ° C., one or more tertiary amines that volatize or decompose without leaving residues between 150 ° C. and 250 ° C., and one or more polar solvents Gelled, wherein the gel does not contain a reaction product of the carboxylic acid component and the amine component.
  4. In the manufacturing method of the paste,
    A method for preparing a paste, characterized in that the gel according to claim 1 or 2 is dispersed together with the solid powder.
  5. In the soldering paste in which the solder powder is dispersed in the gel,
    A gel paste comprising a carboxylic acid component and an amine component gelled in a polar solvent, wherein the gel does not contain a reaction product of the carboxylic acid component and the amine component.
  6. The method of claim 5,
    Lead solder powder is dispersed in the gel according to claim 1 or 2, characterized in that the solder paste.
  7. The method of claim 6,
    A soldering paste, wherein the soldering paste contains a dye.
  8. The method of claim 7, wherein
    Soldering paste, characterized in that the amount of dye is less than 1wt ‰.
  9. A method for soldering and subsequent bonding of constituent members,
    The soldering paste according to claim 5 is remelted for fixing the constituent members,
    And the component is then bonded without a separate cleaning process of the bonding surface by the surface active material or the basic material.
  10. delete
KR1020087011010A 2005-11-08 2006-10-20 Solder pastes comprising nonresinous fluxes KR101105075B1 (en)

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DE102005053553.4 2005-11-08
PCT/EP2006/010139 WO2007054198A2 (en) 2005-11-08 2006-10-20 Solder pastes comprising nonresinous fluxes

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EP1945404B1 (en) 2016-05-11
WO2007054198A2 (en) 2007-05-18
DE102005053553A1 (en) 2007-05-16
EP1945404A2 (en) 2008-07-23
CN101304835B (en) 2013-03-27
JP5334585B2 (en) 2013-11-06
KR20080071984A (en) 2008-08-05
HUE029344T2 (en) 2017-02-28
WO2007054198A3 (en) 2007-07-05
US20090152331A1 (en) 2009-06-18
CN101304835A (en) 2008-11-12
JP2009514683A (en) 2009-04-09
US7926700B2 (en) 2011-04-19

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